High-porosity cellular catalyst having acidic properties to modify colophony
FIELD: organic synthesis catalysts.
SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.
EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.
The present invention relates to a process for producing products of natural resins, such as rosin, and more narrowly to the modification of rosin.
Rosin is a product of primary processing of natural resins, primarily pine oleoresin, and is widely used in various industries. The lack of natural rosin is a high content of unsaturated resin acids, mainly abietic prone to oxidation by the oxygen of the air and the change of physico-chemical properties over time. To overcome this drawback using mainly two methods of modification of rosin: hydrogenation and disproportionation.
Disproportionately rosin significantly more resistant to air oxidation, obtained on the basis of her Soaps are used as emulsifiers for cold polymerization in the production of synthetic rubbers. Disproportionately rosin is also used in the manufacture of adhesives, insulating materials in electrical engineering and for other purposes.
The changing composition of rosin in the disproportionation (reducing the number of acids with conjugated double bonds and the formation of dehydro-, dihydro - and tetrahydroborate) due to the reactions of hydrogenation and dehydrogenation. The latter processes occur when the appreciation is the R temperatures in the presence of various catalysts. Since at high temperatures intensifying processes decarboxylation, leading to deterioration in the quality of the rosin, and the accumulation of gaseous hydrogen, try to decrease this parameter.
The main catalysts for the disproportionation at the present time are the following:
1) iodine, in pure form or with promoters (patent 299080, the Netherlands; patent 2060637, England). The disadvantages of these catalysts are the high cost of iodine, environmental pollution by the products of its transformation (including alkylidene) and the iodine, a significant decrease in acid number, due to decarboxylation at high process temperatures;
2) sulfur and selenium, their oxides and compounds with different media, for example, zeolites (A.S. USSR 763420, Sanderman Century Natural resins, turpentine, taly oil. - M.: Forest industry, 1964, s.257-260). The disadvantages of these catalysts are dark rosin, high toxicity of selenium
3) solid-phase hydrogenation catalysts: mainly metals of the VIII group of the Mendeleev periodic table of elements. The use of Nickel is limited because of its relatively low catalytic activity. In addition, its ability to dissolve the rosin leads to the need for additional purification (distillation) rosin;
4) the biggest rasprostrannyayuschie catalysts based on palladium, the first patents for which were obtained in the 30-ies of the last century. The most famous are the catalysts containing active element is palladium deposited on activated carbon (U.S. Pat. Russia 2055848 and 2081143).
As the catalyst can also be used ion-exchange resin of acid nature (A.S. USSR 1344772).
Gidrirovanny rosin lighter than the original rosin, which determines the possibility of its use in the manufacture of optical glue for lenses, coatings for optical instruments. Wide application gidrirovanny rosin finds in the manufacture of synthetic rubbers, particularly in the production of products that do not contain particulate fillers.
Hydrogenation of rosin exercise for nearly 100 years. The main industrial method currently are catalytic processes. As active agents used Nickel (U.S. Pat. USA 2155039, 2174651, 2739947), rhodium and palladium (U.S. Pat. USA 2346793, 2367287) catalysts. The consumption of hydrogen in the hydrogenation process is 2 mol per one mol of abietic acid.
As a prototype we have chosen the patent of Russia 2055848, according to which for modification (disproportionation) of rosin mixed use catalyst: socialization - cured dehydrated islamochristiana clay Benton is a Hilbert-type and catalyst - palladium charcoal. Melt the rosin is passed sequentially through socialization and then through the catalyst. This provides a residual content of abietic acid at the level of 1-2% at high acid number (there is a slight, 1-3 units decrease in comparison with the original product). The temperature in the catalyst zone 220°C. According to the examples in the patent, the mixing rosin is argon, which leads to significant economic costs. The process was complicated by the destruction and entrainment of catalyst (palladium carbon, which is accompanied not only by a decrease in its catalytic activity, but also by the necessity of separating the resulting product from the fragments of the catalyst.
The object of the present invention is a highly porous honeycomb catalyst with acid properties for modification of rosin. As the base catalyst used highly porous cellular carrier of aluminum oxide (α-Al2About3), and as the active component is characterized by high acidity of sulfated oxides of metals of group IV (TiO2, ZrO2and others) and palladium metal.
Highly porous cellular carrier for catalyst made from open-celled polyurethane foam, soaking the last slip, containing them for more than 30% α -Al2About3, followed by drying at 100 to 200°and annealing at a temperature of 1300-1500°C. during this treatment, the organic basis of completely dries out. The resulting highly porous carrier contains more than 90% α-Al2About3. To develop the surface of the catalyst on its surface causing the oxides of metals of group IV of the Mendeleev periodic Table of elements. For this purpose, the carrier is impregnated with solutions of water soluble salts of zirconium, for example chloride Zirconia or nitrate Zirconia, or a mixture of tetraethoxysilane with isopropyl alcohol, dried at 100-200°and calcined at a temperature of 450 to 950°C. the Content of metal oxide in the catalyst after these operations is 4-10%.
The samples impregnated with a solution of 5-10% sulfuric acid and after drying annealed at a temperature of 550-650°C. the Increase in weight of the catalyst after these operations should be 1-2%.
When further treated with a solution of palladium nitrate, drying and calcination at 450-550°on the surface of the catalyst are 0.5-5% of the oxide of palladium, which, after recovery of molecular hydrogen at room temperature is transformed into metallic palladium.
Produced by this technology the catalyst has a density of 0.3-0.4 g/cm3that corresponds to the porosity of 90-93%, microporosity 20-30%, with the tournament pore size - 0.5 to 2 μm, the mechanical strength of 0.5-2 MPa.
The use of highly porous honeycomb catalyst designed as a single unit, through which passes a flow of rosin and nitrogen or hydrogen, on the one hand, due to the developed surface provides high speed modification, on the other hand, due to the high mechanical strength almost completely eliminates grinding and entrainment of the catalyst.
It is known that solid sulfated oxides of metals of group IV of the Periodic table have a catalytic effect on many electrophilic reactions of the type and in recent years has been widely tested as catalysts in various processes (Krylov, O.V. Solid-phase catalysts. M: ICC academkniga, 2004). Their preparation and properties are discussed in detail in the review Ivanov A.V., Cosnova L.M. Solid supercolony on the basis of zirconium oxide. Grew up with. chem. journal, 2000. T. No. 2. P.21-52, article M. Hino, K. Arata, J. Chem. Soc. Chem. Comm 1980. R-852 and several other publications. However, their independent use in the process of modification of rosin, according to our data, does not provide the necessary positive effect.
The process of modification of rosin successfully runs only when sharing sulfated oxides of high acidity (such as TiO2or ZrO2) and palladium metal; when used is the so called desulfation oxides (TiO 2that α-Al2O3together with palladium degree of disproportionation also dramatically reduced (example 34).
In addition to the above-mentioned advantages of the modular catalyst: no grinding and, therefore, contamination of rosin its fragments, increase service life, the proposed method allows to reduce the temperature of the process of disproportionation 30-40°C. consequently, the reduced decarboxylation of resin acids. A similar positive effect was achieved in the reaction of an alcohol solution of rosin with this catalyst in a hydrogen environment, the lack of the latter (examples 5 and 6).
The method of preparation of the catalyst and the effectiveness of the proposed catalyst of its application can be confirmed by the following examples.
Preparation of open-celled polyurethane foam is made in the form of a cylinder with a diameter of 50 mm and a height of 50 mm was impregnated with the slurry containing 40% α-Al2About3method of cyclic compression and tension, followed by drying at 100 to 200°and annealing at a temperature of 1300-1500°C. during this treatment, the organic basis of completely dries out. The resulting highly porous carrier contains more than 90% α-Al2About3. Then the carrier was impregnated at room temperature with 15% NaCl Zirconia in the water and then you argali at a temperature of 950° C for 1 hour. The content of metal oxide in the catalyst was 7.5%.
The sample obtained at room temperature was soaked with a solution of 10% sulfuric acid (by immersion and subsequent runoff of excess acid without external influence) and after drying was probalily at a temperature of 550-650°C. the Increase in weight of the catalyst after this operation amounted to 1%.
When further treated with a solution of 5% palladium nitrate, drying at 120°C and calcination at 450-550°C on the surface of the catalyst was applied to 2.35% of the oxide of palladium, which, after recovery of molecular hydrogen at room temperature turned into metallic palladium.
Produced by this technology the catalyst contains a 2.0% Pd, has a density of 0.3-0.4 g/cm3that corresponds to the porosity of 90-93%, microporosity 20-30%, the average pore size is 0.5 to 2.0 μm, the mechanical strength of 0.5-2.0 MPa.
In a heated cylindrical reactor with an inner diameter of 50 mm and a volume of 400 ml was placed highly porous honeycomb catalyst in the form of a single block, fixed in the middle of the device. The mass of the catalyst 30 g, the density of 0.38 g/cm, the content of sulfated Zirconia is 8.5%, the content of palladium metal - 2%. In the lower part of the vertically installed reactor load of 25 g of rosin content of abietic sour is 45%, acid number - 172 and create a nitrogen pressure of 0.2 MPa. Turn up the heat and bring the temperature inside the reactor up to 180°C. Then transferred to the reactor in a horizontal position and include longitudinal mixing (rocking). Duration of response 135 minutes, the Apparatus is cooled to 100°With, relieve gas pressure and unload rosin. The content of abietic acid and 0.1%, acid number - 168, color - W.
Similar to example 1. Process temperature 190°C. the Content of abietic acid rosin after the experience of 1.6%.
In the same reactor loaded the unit of catalyst, made of α-Al2O3covered with surface γ-Al2About3total weight 32,4 g, a density of 0.41 g/cm3the content of metallic palladium is 2.6%, and the remaining conditions are identical to example 1. The content of abietic acid rosin after the reaction of 18%.
In the same reactor was loaded with 100 ml of ethanol and 8 g of rosin, the catalytic unit total weight of 31.3 g, the composition of the catalyst similar to the catalyst of example 1, but the content of metallic palladium to 2.8%. The initial hydrogen pressure - 0.17 MPa. The temperature of the experience 115°With, the process time 25 min Flow of hydrogen was 0.92 mol per 1 mol of abietic acid rosin. The content of abietic acid after the reaction is 0%.
Similar is n example 4, but loading a container 12, an Initial hydrogen pressure of 0.3 MPa. The flow of hydrogen to 1.1 mol per mol of abietic acid rosin. The content of abietic acid after the reaction is 0%.
The catalyst for the modification of rosin, characterized in that as the carrier using high porous foam block material based on α-Al2About3and as an active part of the catalyst is sulfated metal oxide of group IV and metal palladium.
FIELD: natural compounds, chemical technology.
SUBSTANCE: invention relates to technology for preparing substances from the natural resins, in particular, to colophony hydrogenation. Method for catalytic hydrogenation of colophony with gaseous hydrogen is carried out on solid catalysts comprising palladium as a metal under enhanced pressure and temperature in the presence of organic solvent. Hydrogenation reaction is carried out in circulating contour wherein hydrogen is dispersed firstly in colophony alcoholic solution and the prepared gaseous-liquid mixture is passed through the catalytic zone filled with the catalyst comprising the highly porous cellular carrier made of aluminum oxide and prepared by the doubling method of polyurethane foam matrix. Method provides the complete elimination of the catalyst grinding, prolonged exploitation working life of catalyst, elimination of loss in separation of the reaction mass from the catalyst and decreasing the pressure value in the process realization.
EFFECT: improved method for hydrogenation.
1 tbl, 1 dwg, 5 ex
FIELD: resin industry.
SUBSTANCE: invention relates to production of polyterpenes, which can be used as oiling agent in manufacture of pressure-sensitive glues, in production of solid and liquid oils, etc. Polyterpene are prepared via continuous polymerization of terpene hydrocarbons in presence of zeolite catalyst by feeding starting hydrocarbons into top section of reactor through perforated cartridge, after which monomer vapors move into catalyst-filled reaction zone at a velocity in full reactor cross-section 0.3-0.4 m/s accompanied by continuous dephlegmation of unconverted part of monomer and returning it into reaction zone. Process is carried out for 7-9 h at 160-170°C. Yield of polyterpenes is 72-80%.
EFFECT: increased uniformity of polyterpene composition (98% dimers).
1 dwg, 1 tbl, 8 ex
FIELD: floatation dressing of non-sulfide ores.
SUBSTANCE: the invention is pertaining to the field of a floatation dressing of non-sulfide ores and may be used in production of floatation reagent-collectors on the basis of fatty acids. The floatation reagent-collector for non-sulfide ores is produced on the basis of saponated fatty acid. Before a saponification of a fatty acid it is heated up to 70-75°С and at stirring action as a regulator of polymerizing inject a phenolic antioxidant Ahydol-1 in amount of 0.5-5 mass %. After the saponification process a produced collector may be added with sodium alkyl sulfate in amount of 4-5 mass %. The flotation collector possesses a high-efficient and high-selective floatation of the non-sulfide ores predominantly barite-containing ores.
EFFECT: the invention ensures production of floatation reagent-collectors on the basis of fatty acids.
4 cl, 1 tbl, 2 ex
FIELD: industrial organic synthesis and catalysts.
SUBSTANCE: invention relates to a methyl ethyl ketone production process via catalytic oxidation of n-butenes with oxygen and/or oxygen-containing gas. Catalyst is based on (i) palladium stabilized with complexing ligand and (ii) heteropolyacid and/or its acid salts, in particular molybdo-vanado-phosphoric heteropolyacid having following composition: H11P4Mo18V7O87 and/or acid salt Na1.2H9.3Mo18V7O87, said complexing ligand being notably phthalocyanine ligand. Catalyst is regenerated by making it interact with oxygen and/or oxygen-containing gas at 140-190°C and oxygen pressure 1 to 10 excessive atmospheres. Oxidation of n-butenes is conducted continuously in two-stage mode at 15 to 90°C in presence of above-defined catalyst.
EFFECT: enhanced process efficiency due to increased stability of catalyst resulting in considerably increased productivity and selectivity.
7 cl, 1 dwg, 3 tbl, 8 ex
FIELD: textile, paper and chemical industries; protection of environment in production of bleachers, biocides and components of oxidizing processes.
SUBSTANCE: proposed catalyst contains one or more metals of platinum group used as active component, one or more polyolefines and activated carbon carrier. It is preferably, that polyolefines have molecular mass above 400 and are selected from ethylene homopolymers and ethylene copolymers with alpha-olefines, propylene homopolymers and propylene copolymers with alpha olefines, butadiene homopolymers and copolymers with styrene and other olefines, isoprene homopolymers and copolymers with other olefines, ethylene-propylene copolymers, ethylene-propylene diolefine three-component copolymers, thermoplastic elastomers obtained from butadiene and/or isoprene and styrene block-copolymers, both hydrogenized and non-hydrogenized. Hydrogen peroxide is produced in presence of said catalyst from hydrogen and oxygen in reaction solvent containing halogenated and/or acid promoter. Proposed catalyst makes it possible to increase degree of conversion and selectivity of process, to obtain aqueous H2O2 solutions at content of acids and/or salts at level of trace amount.
EFFECT: enhanced efficiency.
48 cl, 1 tbl,18 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: preparation of catalyst comprises depositing active components on γ-alumina carrier at stirring, carrier being preliminarily treated with concentrated NaOH solution. Active components are deposited consecutively in three steps. In the first step, preliminarily prepared chitosan in acetic acid solution with KCl solution is deposited for 60-65 min; in the second step, sodium tetrachloropaladate(II) trihydrate Na2PdCl4·3H2O solution is deposited for 60-65 min; and, in the third step, hydrazine hydrate solution as reducing agent is added for 180-240 min. After each step, resulting suspension is filtered off, washed, and dried at 293-303K for 1-2 h in vacuum. Catalyst can be used in chemical industry and in processing of industrial and household wastes.
EFFECT: enhanced nitrate hydrogenation efficiency.
6 cl, 1 dwg, 6 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.
EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.
1 dwg, 1 tbl, 12 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.
EFFECT: deepened oxidation of hydrocarbons.
5 cl, 1 tbl, 4 ex
FIELD: supported catalysts.
SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.
EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.
5 cl, 9 ex
FIELD: petrochemical synthesis catalysts.
SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.
EFFECT: increased selectivity and activity of catalyst.
2 cl, 2 tbl, 21 ex
FIELD: organic chemistry, chemical technology, catalysts.
SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.
EFFECT: improved preparing method.
14 cl, 1 tbl, 6 ex
FIELD: gas treatment catalysts.
SUBSTANCE: invention provides catalyst consisted of inert carrier and catalytic coating containing platinum, rhodium, and oxide substrate, wherein catalytic coating includes: (i) at least one first substrate material selected from group consisted of first active aluminum oxide enriched with cerium oxide; mixed oxide, which is cerium oxide/zirconium dioxide; and zirconium dioxide component; provided that catalytic component in at least one first substrate material is first portion of the total quantity of catalyst platinum, wherein concentration of the first portion of the total quantity of catalyst platinum lies within a range of 0.01 to 5.0% of the total mass of catalyst-containing materials; and (ii) a second substrate material containing second portion of total quantity of platinum and rhodium as catalytic component, said second substrate material being second active aluminum oxide, wherein concentration of platinum plus rhodium on the second substrate material lies within a range of 0.5 to 20% of the total mass of the second substrate material. Method for preparing above catalyst is also provided.
EFFECT: increased catalytic activity and reduced catalyst preparation expenses.
17 cl, 3 dwg, 5 tbl, 3 ex